Overview of EPA Method 1631 Revision E By

Overview of EPA Method 1631, Revision E By Roy W. Byrd Division of Water Quality Laboratory Section Metals Unit

Background Slide 2 u. EPA Method 1631: Mercury in Water by Oxidation, Purge and Trap, and Cold Vapor Atomic Fluorescence Spectrometry Applicable to determination of Hg at Water Quality Criteria (WQC) levels u. Supports implementation of National Toxics Rule and Great Lakes Water Quality Initiative u. Interlaboratory validation study completed prior to proposal -Joint effort with the Electric Power Research Institute (EPRI) -Twelve participating laboratories / One referee laboratory -Validated in reagent water, freshwater, effluent, marine water u

Background (cont. ) Slide 3 u. EPA developed Method 1631 for determining mercury levels in the low ng/L range (approximately 400 times more sensitive than other approved methods) Method 1631, Revision A was proposed on May 26, 1998 (63 FR 28868) u. Method 1631, Revision B was promulgated on June 8, 1999 (64 FR 30417) u. Method 1631, Revision C was promulgated on June 18, 2001 u. Method 1631, Revision E was promulgated on October 29, 2002 u

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Slide 5 u. EPA Method 1631 is “performance-based” Changes that do not compromise method performance are allowed u. Changes to improve performance or reduce measurement costs are allowed u u Examples of allowable changes: -Automation of dual-amalgamation system -Single-trap amalgamation -Changes in bubbler design -Use of CVAAS if less sensitivity is acceptable Additional Information “Method 1631: Guidelines Establishing Test Procedures for the Analysis of Pollutants; Measurement of Mercury in Water” on the WEB at http: //www. epa. gov/ost/methods/1631. html

Clean Techniques Review u. General requirements u Clean sampling and storage procedures u Clean sample handling procedures in field and lab u Use of clean bench or a clean room u Comprehensive QA/QC program Level of cleanliness needed may vary, depending on target concentration and sampling location u u Analysis of blanks, and more blanks Slide 6

u. Blanks in Revision E u u u u Slide 7 Bottle Blank – The bottle blank is used to demonstrate that the bottle is free from contamination prior to use. Bubbler Blank – For this Method, the bubbler blank is specific to the bubbler system and is used to determine that the analytical system is free from contamination. Equipment Blank – Reagent water that has been processed through the sampling device at a laboratory or other equipment cleaning facility prior to shipment of the sampling equipment to the sampling site. Field Blank – Reagent water that has been transported to the sampling site and exposed to the same equipment and operations as a sample at the sampling site. The field blank is used to demonstrate that the sample has not been contaminated by the sampling and sample transport systems. Method Blank - Method blanks are used to determine the concentration of mercury in the analytical system during sample preparation and analysis, and consist of a volume of reagent water that is carried through the entire sample preparation and analysis. Reagent Blank-Reagent blanks are used to determine the concentration of mercury in the reagents (Br. Cl, NH 2 OH-HCl, and Sn. Cl 2) that are used to prepare and analyze the samples. System Blank— For this Method, the system blank is specific for the flow-injection system and is used to determine contamination in the analytical system and in the reagents used to prepare the calibration standards.

• Quality Control Requirements (Blanks) Slide 8

Quality Control Requirements (cont. ) Slide 9

Rule on Field Blanks Slide 10 EPA Method 1631, Revision E - September 2002 “ 12. 5. 2 Report results for Hg in samples, method blanks and field blanks separately. In addition to reporting results for the samples and blank(s) separately, the concentration of Hg in the method blanks or field blanks associated with the sample may be subtracted from the results for that sample, or must be subtracted if requested or required by a regulatory authority or in a permit. ” Interferences “ 4. 4. 1. . At the time of promulgation of this Method, gold and iodide were known interferences. At a mercury concentration of 2. 5 ng/L and at increasing iodide concentrations from 30 to 100 mg/L, test data have shown that mercury recovery will be reduced from 100 to 0 percent. ”

Table 3 (1) Slide 11 Precision and Recovery for Reagent Water, Fresh Water, Marine Water, and Effluent Water Using Method 1631

Why Bother? Slide 12 u. Town of Falmouth, Maine conducted a study in 1998* – Historical Methods (Method 245. 1) results were < 220 ppt(ng/L) Hg – Method 1631 results were 62. 9 ppt (ng/L) Hg – Method 1631 with Method 1669 results were 15. 3 ppt (ng/L) Hg – *Courtesy of Judy Schofield of Dyn. Corp, Science and Engineering Group